This invention relates to compositions of matter known in the art of chemistry as inhibitors or retarders of scorch or premature onset of cure (crosslinking) during the compounding and subsequent processing in the presence of free radical initiators of thermoplastic polymers, elastomeric polymers or mixtures of said polymers which are capable of cure by such free radical initiators, mixtures of such inhibitors of scorch with the free radical initiators, to processes for their manufacture and use as well as to polymeric compositions containing such inhibitors of scorch and to curable compositions comprising such inhibitors of scorch, free radical initiators and at least one polymeric material capable of cure by a free radical initiator.
Free radical initiators (Organic peroxides and, optionally, certain azo initiators) are used in crosslinking thermoplastic polymers and elastomers and their mixtures when the final products are required to meet high mechanical and physical requirements, such as improved thermal aging and lower residual (permanent) deformation under pressure compared with uncrosslinked thermoplastics and/or sulfur cured elastomers.
Since both thermoplastics and elastomers are solid materials at normal room temperatures, in order to add the free radical crosslinking agent and any other desired ingredients such as dyes, pigments, fillers, antioxidants, UV and heat stabilizers and the like into the polymer, the polymers must be mechanically mixed with the free radical crosslinking agent and any of the other desired ingredients at temperatures sufficiently elevated to allow the polymers to flow in the mixing equipment.
The crosslinking period and the time from the addition of the free radical initiator up to incipient cross linkage (scorch time) are dependent on the thermal decomposition rate (conveniently expressed as the half-life period) of the free radical initiators employed as crosslinking agents.
Obviously, the longer the processing time before onset of scorch that can be provided to a manufacturer without sacrifice of final crosslink speed or density, the more beneficial it will be because with conventional methods of mixing or compounding, such as milling, Banbury, or extrusion scorch begins when the time and temperature relationship results in the initiation of decomposition of the free radical initiator. If this occurs too soon, gel particles in the mass of polymer to be compounded may be formed thereby producing inhomogeneity in the final product. Excessive scorch reduces the plastic properties of the material so that it can no longer be processed, thus, resulting in loss of the entire batch.
These have been a number of approaches attempted to extend scorch time and these are discussed in what applicants consider to be the two most pertinent prior art references cited below. Other pertinent art is discussed in those references, but such art is really only of background interest for this invention.
Groepper, et al., in U.S. Pat. No. 5,245,084 discloses the use of organic peroxides suitable for crosslinking thermoplastics and elastomers in combination with a specific group of hydroquinones and a crosslinkage promoter selected from the usual crosslinkage promoters normally used in these applications. One specific purpose of his invention is the avoidance of the presence of sulfur releasing compounds in the polymers to be processed while extending the scorch time without adversely affecting cure time or cure density. The use of hydroquinone mono alkyl or aryl ethers is neither taught nor suggested.
Novits et al., in U.S. Pat. No. 6,197,231B1 teaches an improvement over Groepper. The use of a combination of free radical initiators (either organic peroxides or a specific class of azo initiators) in combination with hydroquinones, crosslinkage promoters and known sulfur releasing sulfur accelerators for sulfur cure of elastomers is taught for extending scorch time without adverse effects on cure time or cure density for thermoplastics, elastomers and their mixtures is taught. Hydroquinone mono alkyl and aryl ethers are included in the hydroquinones listed as suitable for use, but their use without the sulfur accelerators is not suggested nor is the advantage found by applicants for such use suggested by either reference. For wire and cable insulation and some other uses, the presence of sulfur is not desired because it may affect insulation value and/or discolor metals it is in contact with.
The invention provides in a composition aspect, a mixture for crosslinking thermoplastic, elastomeric and mixtures of thermoplastic and elastomeric polymers capable of being crosslinked by free radical initiators providing extended scorch time during compounding, without adverse effect on final crosslink time or crosslink density consisting essentially of
a) at least one free radical initiator suitable for crosslinking such polymers selected from the group consisting of organic peroxides and azo initiators;
b) at least one hydroquinone mono alkyl or aryl ether;
c) at least one allylic crosslinkage promoter.
The composition aspects of the invention possess the inherent applied use characteristic of being scorch retarders when employed during compounding of thermoplastic, elastomeric and mixtures of thermoplastic and elastomeric polymers capable of cure by free radical initiators while having no adverse effect on the cure time or cure density of such polymers and also have minimal adverse effects on the color of such polymers after cure.
Special mention is made of aspects of the invention wherein the hydroquinone mono alkyl ether is hydroquinone monomethyl ether, which composition has been shown to have the least adverse effect on color.
The invention also contemplates a mixture prepared by mixing the three ingredients of the composition together as the essential ingredients in any order either prior to or during addition to the polymers.
By xe2x80x9cconsisting essentially ofxe2x80x9d is meant that the mixture modified by the expression does not contain scorch retarder ingredients previously employed as such, except for those ingredients specifically named, but the presence of other conventional polymer additives such as antioxidants, heat and light stabilizers, plasticizers and the like are not excluded. Provided the hydroquinone mono alkyl or mono aryl ether is present the presence of a second hydroquinone of the type described in the Groepper patent is permitted.
By xe2x80x9cthermoplastic, elastomeric and mixtures of thermoplastic and elastomeric polymers curable or crosslinkable with free radical initiatorsxe2x80x9d is meant all those solid polymers which meet that description but excluding such polymers as polypropylene and mixtures of solid polymers containing 20% or more polypropylene which are known not to be susceptible to cure or crosslinking with free radical initiators selected from organic peroxides and azo initiators.
The starting materials for the manufacture of the compositions contemplated by the invention are all well known compounds and are either commercially available or may be prepared by synthetic techniques well known in the art.
The superior scorch resistance with no adverse effect on cure time, crosslink density or color for free radical initiator curable thermoplastic and/or elastomeric polymers may be obtained by admixing, conveniently by employing conventional compounding means, with such polymer(s) wherein crosslinking is desired, a scorch retarding/crosslinking composition of the composition aspect of the invention.
The scorch retarding/crosslinking composition may preferably be blended into the desired polymers as a preformed mixture or the individual ingredients may be added individually or as subcombinations of one or more of the ingredients. It is preferred that in the latter two cases the hydroquinone or the hydroquinone and the crosslinkage promoter be added to the polymer before the addition of the free radical initiator.
Free Radical Initiators
In accordance with the present invention, compounds well known in the art as azo initiators and/or organic peroxides (with the exception of hydroperoxides and peroxydicarbonates) which upon thermal decomposition generate free radicals that facilitate the curing/crosslinking reaction may be employed.
Detailed listings of such initiators are provided in U.S. Pat. Nos. 5,245,084 and 6,197,213B1 and the references cited therein as are detailed conditions of use and proportional amounts by weight to employ in the curing of the polymers.
Suitable polymers and copolymers are also listed in the same two patents and the references cited therein.
The allylic monomer crosslinking agents such as triallyl cyanurate, triallyl phosphate, allyldiglycol and the like cited in the same two patents are those contemplated for use in the invention in the proportion by weight quantities given in those two patents.
The hydroquinone mono alkyl and mono aryl ethers are all well known compounds and may be used in the proportions by weight given in U.S. Pat. No. 6,197,213B1.
Typical examples are:
hydroquinone monomethyl ether,
hydroquinone monobenzyl ether,
hydroquinone mono phenyl ether,
hydroquinone monoethyl ether and,
hydroquinone monopropyl ether.
The alkyl and aryl groups are not contemplated as exceeding 10 carbon atoms. Hydroquinone monomethyl ether is preferred.
The crosslinking/scorch retarding compositions of this invention are homogeneous meltable solids if the peroxide is a solid at ambient temperature, or a liquid if the peroxide is a liquid at ambient temperature. Solid compositions may be ground by standard methods into free flowing powders for convenience in addition to polymer compositions, or, if desired, polymeric master batches may be prepared by melt blending the scorch retarding/crosslinking compositions as concentrates into carrier polymers compatible with or identical in composition to the polymer which is to be compounded and cured. The master batches may also be prepared on inert fillers as carriers.
The following Examples further illustrate the best mode contemplated by the inventors for the practice of their invention.
Peroxide compositions were prepared and then absorbed onto cable grade polyethylene in glass jars. The jars were place in a 70xc2x0 C. hot air oven to accelerate absorption. These prepared samples were used for color and crosslinking evaluation work. Crosslinking evaluation work was conducted using a Moving Die Rheometer (Alpha Technologies MDR 2000E) which was interfaced to an IBM type personal computer for raw data collection and computation. Temperatures and degrees of arc employed are provided in the data tables. The rheometer creates a very uniform, consistent flat crosslinked disk which was subsequently used to measure final cured polyethylene color.
Color measurements were conducted using a HunterLab ColorQUEST Sphere Spectrocolorimeter. The Spectrocolorimeter was standardized using Reflectance-Specular Included (RSIN) using the SAV (small angle view lens) and UV included, together with specially supplied black, white and gray standard color plaques provided by the manufacturer. Color measurements were made using the centermost portion of the MDR cured specimen as this represents an exact thickness dimension, relating to a present die gap on the instrument which is calibrated by Alpha Technologies Engineers on a regular basis as part of the instrument certification maintenance program. Color data reported in the data tables are b* and YID. The b* is a measurement of the yellowness for positive values or blueness for negative b* values, of a measured specimen. When the b* is in the positive range (as in the case of our data) this is the chromaticity color intensity. Furthermore YID data was also measured with this instrument. YID or yellowness index is a color measurement associated with changes in polymer degradation. The higher the YID value, the more yellow color intensity exists for that product, conversely lower YID numbers mean that the sample exhibits lower yellow color.
In our peroxide composition examples we provide mixtures of other hydroquinones used in combination with an ether type hydroquinone as taught in the practice of our invention. This was done because of the poor solubility of the other hydroquinones in the peroxide, in conjunction with their inherent inefficiency to provide increase scorch time protection, compared to the singular use of hydroquinone monomethyl ether. We found that unexpectedly the other hydroquinone compounds will precipitate or separate from the peroxide upon standing, which would then provide inconsistent and harmful effects upon the crosslinking and electrical properties of a high voltage cable insulation. In summary our color and crosslinking performance data shows that the use of dicumyl peroxide, hydroquinone monomethyl ether and TAC provides equal weight crosslinking performance to a cable grade dicumyl peroxide, while providing the best overall scorch time performance with a final color, superior to even the use of the cable grade dicumyl peroxide alone. The totality of these unexpected advantages, makes this peroxide composition particularly useful for wire and cable applications.
Peroxide, Ether Quinone and Coagent Composition Ratios
The ether quinone to allylic coagent maximum ranges are: 100:1 to 1:100. The peroxide to (ether quinone and allylic coagent) blend maximum ranges are: 1:50 to 50:1. The ether quinone to allylic coagent preferred ranges are: 5:1 to 1:5, preferably 1:1 to 1:5. The peroxide to (ether quinone and allylic coagent) blend preferred ranges are: 1:3 to 10:1; most preferably 3:1 to 7:1 (all by weight).